JP5225528B2 - Method for producing silicon-containing polymer - Google Patents

Description

  The present invention relates to a curable composition. Specifically, the present invention relates to a curable composition having excellent stability, transparency, and curing performance, and further, the cured product having various physical properties such as heat resistance, solvent resistance, alkali resistance, weather resistance, optical properties, and electrical properties. .

  Various research has been conducted on composite materials combining organic and inorganic materials, and industrially, coating methods that combine inorganic fillers with organic polymers or modify metal surfaces with organic polymers Etc. are used. In these composite materials, the material constituting them has a size of the order of micron or more, so although some physical properties can be improved, many performances are simply additive rules of both. It shows only the expected value.

  On the other hand, in recent years, organic and inorganic composite materials in which the domain size of each material is in the order of nanometers and combined at the molecular level have been actively studied. Such materials are expected not only to have the characteristics of each material, but also to be a new functional material that is completely different from each material and has the advantages of both that cannot be predicted by the Additive Law.

  Such an organic / inorganic composite material has a chemical bond type in which one material and the other material are mixed at the molecular level via a covalent bond, and one material is used as a matrix and the other material is finely contained therein. There are mixed and mixed types. This simple dispersion / combination mixed type does not have strong bonds between the two materials, so that separation occurs or, for example, when used as a cured material, various physical properties such as heat resistance and solvent resistance are not improved. It may be enough.

On the other hand, the sol-gel method is often used as a method for synthesizing inorganic materials. The sol-gel method is a reaction in which a crosslinked inorganic oxide is obtained at a low temperature by hydrolysis of precursor molecules and subsequent polycondensation reaction.
The inorganic material obtained by this sol-gel method has a problem of poor storage stability, such as gelation in a short period of time. The Journal of Chemical Society of Japan, 1998 (No. 9), 571 (1998) pays attention to the difference in condensation rate due to the chain length of the alkyl group of trialkoxyalkylsilane. Add alkoxy long-chain alkyl silane to seal silanol groups in polysiloxane, and then add acetylacetone when a predetermined molecular weight is reached by condensation reaction of methyltrimethoxysilane using an aluminum catalyst. Attempts to improve storage stability through ligand exchange in the reaction system. However, these methods have been insufficient in improving storage stability.

Problems to be solved by the invention

  The object of the present invention is excellent in stability, transparency and curing performance, and the cured product is excellent in various physical properties such as heat resistance, solvent resistance, alkali resistance, weather resistance, optical properties, electrical properties, etc. It is in providing the curable composition characterized by containing a containing polymer.

Means for solving the problem

  As a result of diligent investigation focusing on the storage stability and the like of the silicon-containing polymer, the present inventors have a specific reactive group as an essential component, no silanol group, Si—O—. Attention was focused on silicon-containing polymers having one or more cross-linked structures with Si bonds and having a molecular weight of 500 to 1,000,000.

That is, the present invention relates to Si—OR ¹ , Si—CH═CH ₂ , Si—R ² —CH═CH ₂ , Si—H, Si—R ² —NH ₂ , Si—R ² —OCOC (R ³ ) = CH ₂ and Si—R ² —OH group [wherein R ¹ is an alkyl group having 1 to 5 carbon atoms, R ² is an alkylene group or phenylene group having 1 to 9 carbon atoms, and R ³ is hydrogen or a methyl group. ] One or two or more reactive groups A selected from the group consisting of: No Si-OH group, one or more cross-linked structures with Si-O-Si bonds, and a molecular weight of 500 to 1,000,000 A method for producing a silicon-containing polymer of
After obtaining a polymer by hydrolyzing / condensing alkoxysilane or chlorosilane having a reactive group A, the polymer is a kind selected from the group consisting of orthoformate ester, orthoacetate ester, tetraalkoxymethane and carbonate ester Alternatively, the present invention provides a method for producing a silicon-containing polymer, wherein two or more hydrolyzable ester compounds are added, and the Si—OH group of the polymer is sealed by stirring and heating .

DETAILED DESCRIPTION OF THE INVENTION
In the present invention, Si—OR ¹ , Si—CH═CH ₂ , Si—R ² —CH═CH ₂ , Si—H, Si—R ² —NH ₂ , Si—R ² —OCOC (R ³ ) ═CH ₂ Contact and Si-R ² -OH group [wherein, R ¹ represents an alkyl group having 1 to 5 carbon atoms, R ² is an alkylene group or a phenylene group having 1 to 9 carbon atoms, R ³ is hydrogen or a methyl group ] One or two or more reactive groups A selected from the group consisting of: No Si-OH group, one or more cross-linked structures with Si-O-Si bonds, and a molecular weight of 500 to 1,000,000 These silicon-containing polymers are used. The reactive group A may be a reactive group of anti応基A or between other compounds (e.g., later-described reactive group B), a reaction to form a chemical bond. In the silicon-containing polymer, the crosslinking by the Si—O—Si bond may be at least one place in the silicon-containing polymer used in the present invention. Specifically, as the structure having these crosslinking, It is mentioned that it has a ladder-like (ladder-like), cage-like, annular, etc. structure formed by Si—O—Si bonds, and all of the ladder-like, cage-like, annular, etc. structures are Si. You may be comprised by the -O-Si bond and one part may be formed by the Si-O-Si bond. Of course, a plurality of Si-O-Si bonds may be repeated.

When the silicon-containing polymer used in the present invention has a Si—OR ¹ group [wherein R ¹ is an alkyl group having 1 to 5 carbon atoms], the Si—OR ¹ group [wherein R ^{1 is} Is an alkyl group having 1 to 5 carbon atoms] or an alkoxysilane obtained by hydrolysis / condensation reaction of chlorosilane and having a reactive group A other than Si-OR ¹ group. It can also be obtained by appropriately selecting a mixture with chlorosilane and subjecting it to hydrolysis / condensation reaction. Furthermore, you may make it react in an alcohol solvent as needed, and you may process with a hydrolysable ester compound. It can also be obtained by using a silicon dioxide condensate after removing sodium from sodium silicate by ion exchange or the like.

Is a reactive group A other than Si-OR ¹ _{group, Si-CH = CH 2,} Si-R 2 -CH = CH 2, Si-H, Si-R 2 -NH 2, Si-R 2 -OCOC (R _{^{3) = CH 2, S i}} -R 2 -OH case of silicon-containing polymer of the present invention having a group, alkoxysilane or chlorosilane or Si-oR ¹ group, with a reactive group a other than Si-oR ¹ group It is obtained by appropriately selecting a mixture of alkoxysilane or chlorosilane having a reactive group A other than chlorosilane and an alkoxysilane or chlorosilane having no reactive group A other than Si-OR ¹ group, and subjecting it to hydrolysis / condensation reaction.

In the reaction using an alkoxysilane and chlorosilane having a reactive group A other than ¹ group the Si-OR, in consideration of the inorganic nature resulting silicon-containing polymer, alkoxy having reactive groups A other than Si-OR ¹ group It is preferable to carry out a hydrolysis / condensation reaction by mixing silane with alkoxysilane or chlorosilane having no reactive group A other than Si-OR ¹ group.

Examples of the alkoxysilane and chlorosilane having a reactive group A other than Si-OR ¹ group used in the present invention, it is sufficient with a reactive group A other than Si-OR ¹ group in the molecule, for example, ( 3-acryloxypropyl) methyldimethoxysilane, (3-acryloxypropyl) trimethoxysilane, allyldimethoxysilane, allyltrimethoxysilane, allyltriethoxysilane, aminophenyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3 -Aminopropyltriethoxysilane, butenyltriethoxysilane, 2-cyanoethyltriethoxysilane, 2-cyanoethyltrimethoxysilane, 3-cyanopropylmethyldimethoxysilane, 3-aminopropylmethyldimethoxysilane, 3-cyanopropyltriethoxysilane Hydroxymethyltriethoxysilane, methacryloxymethyltriethoxysilane, methacryloxymethyltrimethoxysilane, methacryloxypropyltriethoxysilane, methacryloxypropyltrimethoxysilane, methyldiethoxysilane, methyldimethoxysilane, phenyldiethoxysilane, Instead of triethoxysilane, vinylmethyldiethoxysilane, vinylmethyldimethoxysilane, vinyltriethoxysilane, vinyltrimethoxysilane, and each of these alkoxy compounds, all of the hydrogen atoms of these alkoxysilanes and chlorosilanes or Examples thereof include a deuteride partially deuterium or a fluorinated fluoride atom, and one or more of these can be used. Further, in the case of a silicon-containing polymer having a reactive group A other than the Si-OR ¹ group, it includes those in which at least two other substituents bonded to the silicon atom in the reactive group A are oxygen atoms. It is preferable.

Examples of alkoxysilanes and chlorosilanes that do not have a reactive group A other than Si-OR ¹ groups used in the present invention include acetoxymethyltrimethoxysilane, benzyltriethoxysilane, bis (triethoxysilyl) methane, Bis (triethoxysilyl) ethane, bis (triethoxysilyl) hexane, 3-bromopropyltrimethoxysilane, butyltrimethoxysilane, chloromethyltriethoxysilane, chlorophenyltriethoxysilane, 3-chloropropyltrimethoxysilane, diethyldi Ethoxysilane, dimethyldiethoxysilane, dimethyldimethoxylane, dodecyltrimethoxysilane, ethyltriethoxysilane, ethyltrimethoxysilane, butyltrimethoxysilane, methoxypropyltrimethoxysilane, methyl Triethoxysilane, methyltrimethoxysilane, octyltrimethoxysilane, phenylmethyldiethoxysilane, phenylmethyldimethoxysilane, phenyltriethoxysilane, phenyltrimethoxysilane, tetraethoxysilane, tetramethoxysilane, tolyltrimethoxysilane, diphenyldimethoxy Instead of silane, diphenyldiethoxysilane, trimethylmethoxysilane, trimethylethoxysilane, triethylethoxysilane, triphenylethoxysilane, and their respective alkoxy compounds, all or one of the hydrogen atoms of these alkoxysilanes and chlorosilanes are used. Examples include deuterated compounds whose parts are deuterium or fluorinated compounds having fluorine atoms, and one or more of these may be used. You can. When the reactive group A is a Si-OR ¹ silicon-containing polymer, the alkoxysilane having no reactive group A other than the Si-OR ¹ group is bonded to the silicon atom to which the alkoxy group is bonded. Preferably, the other at least two substituents are oxygen atoms.

Compounding ratio of the alkoxysilane having no reactive group A other than alkoxysilane and Si-OR ¹ group having a reactive group A other than Si-OR ¹ group is a molar ratio of 0: 100 to 100: 0 is preferred. More preferably, it is 5: 95-95: 5.

  In the silicon-containing polymer of the present invention, the other at least two substituents bonded to the silicon atom in the reactive group A are preferably oxygen atoms.

The alkoxysilane having a reactive group A other than the Si-OR ¹ group and the alkoxysilane having no reactive group A other than the Si-OR ¹ group may be treated with an alcoholate or complex of another metal, if desired. In combination with them, hydrolysis and condensation reactions are performed, and metals other than silicon, such as boron, magnesium, aluminum, phosphorus, titanium, iron, zinc, zirconium, niobium, tin, tellurium, tantalum, etc., are incorporated into the silicon-containing polymer. It is also possible.

  In the present invention, the hydrolysis / condensation reaction of alkoxysilane or chlorosilane may be carried out by so-called sol-gel reaction. As such sol-gel reaction, hydrolysis with acid or base or other catalyst is carried out without solvent or solvent. Examples include a method of performing a decomposition / condensation reaction. The solvent used at this time is not particularly limited, and specific examples include water, methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, t-butanol, acetone, methyl ethyl ketone, dioxane, tetrahydrofuran and the like. 1 type of these can be used, and 2 or more types can also be mixed and used.

  In the hydrolysis / condensation reaction of the alkoxysilane or chlorosilane, the alkoxysilane or chlorosilane generates a silanol group (SiOH group) by hydrolysis with water, and the generated silanol groups, or the silanol group and the alkoxy group Proceed by condensation. In order to advance this reaction, it is preferable to add an appropriate amount of water. Water may be added to the solvent, or the catalyst may be added after dissolving in water. In addition, the hydrolysis reaction also proceeds due to moisture in the air or a small amount of moisture contained in the solvent.

  The catalyst such as acid or base used in the hydrolysis / condensation reaction is not particularly limited as long as it promotes the hydrolysis / condensation reaction. Specifically, inorganic acids such as hydrochloric acid, phosphoric acid, sulfuric acid and the like are used. Organic acids such as acetic acid, p-toluenesulfonic acid and monoisopropyl phosphate; inorganic bases such as sodium hydroxide, potassium hydroxide, lithium hydroxide and ammonia; amine compounds such as trimethylamine, triethylamine, monoethanolamine and diethanolamine Titanium esters such as tetraisopropyl titanate and tetrabutyl titanate; Tin carboxylates such as dibutyltin laurate and octylstannic acid; Boron compounds such as trifluoroboron; Chlorination of metals such as iron, cobalt, manganese and zinc And metal carboxylates such as naphthenates or octylates; Mini um aluminum compound tris acetyl acetate, etc., and the like, also the use of these one may be used in combination of two or more. A preferred example is a method in which an acid catalyst is added and the reaction is allowed to proceed under acidic conditions (pH 7 or lower), and then a base catalyst is added to carry out the reaction under neutralization or basicity.

The order of the hydrolysis-condensation reaction is not particularly limited, in the case of silicon-containing polymer having a reactive group A other than Si-OR ¹ group, and an alkoxysilane having a reactive group A other than Si-OR ¹ group Si- An alkoxysilane having no reactive group A other than the OR ¹ group may be mixed to perform a hydrolysis / condensation reaction, or an alkoxysilane having no reactive group A other than the Si-OR ¹ group alone. Further, after some hydrolysis / condensation reaction, an alkoxysilane having a reactive group A other than Si-OR ¹ group may be added to perform further hydrolysis / condensation reaction, and conversely, other than Si-OR ¹ group Even if alkoxysilane having a reactive group A alone is subjected to hydrolysis / condensation reaction to some extent, alkoxysilane having no reactive group A other than Si-OR ¹ group is added to perform hydrolysis / condensation reaction. Good. Of course, ^one or a mixture of two or more alkoxysilanes and chlorosilanes having a reactive group A other than the Si-OR1 group may be subjected to a hydrolysis / condensation reaction. In the case of obtaining the silicon-containing polymer having no reactive group A other than Si-OR ¹ group has no reactive group A other than Si-OR ¹ group alkoxysilane and one or two or more mixtures of chlorosilanes May be subjected to hydrolysis / condensation reaction.

  In order to obtain the silicon-containing polymer produced by the hydrolysis / condensation reaction, the reaction solvent, water, and catalyst may be removed. For example, after adding a solvent such as butanol to extract the solvent, the extraction solvent is placed under a nitrogen stream. Can be distilled off under reduced pressure. In addition, the solution after the hydrolysis / condensation reaction may be subjected to a treatment with a hydrolyzable ester and a treatment for obtaining a curable composition as it is or after a catalyst removal treatment.

  The molecular weight of the silicon-containing polymer used in the present invention is, in terms of polystyrene, a weight average molecular weight of 500 to 1,000,000, preferably 1,000 to 100,000. If it is smaller than 500, desirable physical properties cannot be obtained, and if it is larger than 1,000,000, it cannot be combined at the nanometer level and molecular level, and the product becomes non-uniform or opaque and sufficient physical properties are obtained. Absent.

  The number of reactive groups A in the silicon-containing polymer used in the present invention is not particularly limited depending on the molecular weight of the resulting silicon-containing polymer, but one or more per molecule of silicon-containing polymer, One per highest silicon atom is required. If it is less than this, chemical bonding with the linear compound having the reactive functional group B is not performed, and if it is more than this, so-called inorganicity (inorganic physical properties) decreases due to the reactive group in the silicon-containing polymer.

The silicon-containing polymer having the reactive group A, which is an essential constituent component of the present invention, does not have a Si—OH group (silanol group). However, the silanol group is blocked by treating with a hydrolyzable ester compound. Storage stability can be significantly improved. As the hydrolyzable ester compound, orthoformate ester, orthoacetate ester, tetraalkoxymethane, carbonate ester and the like can be used, and orthoformate trialkyl ester, tetraalkoxymethane and the like are particularly preferable.
It is also possible to obtain a silicon-containing polymer having no Si—OH group by adjusting the reaction conditions such as the catalyst for hydrolysis / condensation reaction, temperature, reaction time, and charging amount.

  The treatment method with a hydrolyzable ester is a linear compound having a silicon-containing polymer as a constituent component, a state in which a silicon-containing polymer and a solvent are mixed, or a silicon-containing polymer and a reactive functional group B. Or a mixture of a silicon-containing polymer and a linear compound having a reactive functional group B and a curing catalyst, an excess amount of a hydrolyzable ester may be added, and stirring and heating are performed at that time. It is preferable to do. After the treatment, unreacted hydrolysable ester may be removed by heating and decompressing under a nitrogen stream. This treatment eliminates silanol groups and improves storage stability. Of course, it is important that the amount of reactive groups in the silicon-containing polymer be unaffected by processing.

The linear compound having the reactive group B used in the present invention is not limited, but it must have a functional group that reacts with the reactive group A of the silicon-containing polymer, and has a low molecular weight having one or more reactive groups in the molecule. Compounds and polymer compounds can be used. In addition, a reactive group may be chemically bonded to the polymer compound as appropriate. Examples of reactive groups B are H—Si— group, HO—Si— group, R ¹ O—Si— group, CH ₂ ═C (R ³ ) — group, CH ₂ ═C (R ³ ) —R. ² -groups, CH ₂ ═C (R ³ ) —COO— (R ² ) — groups, hydroxyl groups, epoxy groups, alicyclic epoxy groups, etc. [wherein R ¹ is alkyl having 1 to 5 carbon atoms. Group, R ² is an alkylene group having 1 to 9 carbon atoms or a phenylene group, and R ³ is hydrogen or a methyl group]. Polymer compounds include dimethylpolysiloxane, diphenylpolysiloxane, dimethylsiloxane / diphenylsiloxane copolymer, polyimide resin, polyalkylene glycol such as polyethylene glycol and polypropylene glycol, polyurethane resin, epoxy resin, phenol resin, polyester, melamine resin, polyamide Examples thereof include resins.

  The curing catalyst used in the present invention is not limited by the type of reactive group or the curing method. For example, as a catalyst for the Si-OR condensation reaction, bis (2-ethylhexanoate) tin, bis (neodecanoate) tin, di-n-butylbutoxychlorotin, di-n-butyldiacetoxytin, di-n -Tin butyl dilaurate, tin dioctyl dilaurate, etc. are mentioned. Examples of the Si—H addition reaction catalyst include a platinum-carbonylvinylmethyl complex, a platinum-divinyltetramethyldisiloxane complex, a platinum-cyclovinylmethylsiloxane complex, and a platinum-octylaldehyde complex. Two or more of these curing catalysts can be used in combination.

In order to obtain the curable composition of the present invention, a silicon-containing polymer and, if necessary, a linear compound having a reactive group B and / or a curing catalyst are mixed, and a treatment such as heating with the used curing catalyst or the like. I do.
There is no particular limitation on the mixing method, for example, a method of mixing a silicon-containing polymer and a linear compound having a reactive group B immediately before use, or adding a curing catalyst and heating when mixing and performing a curing reaction in advance. The method of making it harden | cure by process etc., the method of making it harden | cure by heating etc. when mixing all beforehand and performing hardening reaction etc. are mentioned.

  The silicon-containing polymer of the present invention does not undergo modification during storage or increase in molecular weight, and is excellent in storage stability. In particular, the storage stability of a silicon-containing polymer treated with a hydrolyzable ester compound is particularly excellent.

  The blending ratio of the curable composition of the present invention may be appropriately adjusted according to the physical properties of the cured product to be obtained, but has the characteristics of both a silicon-containing polymer and a linear compound having a reactive group B. In order to obtain an excellent composite material, the weight ratio of silicon-containing polymer: linear compound = 100: 0 to 1:99 is preferable.

When the curable composition of the present invention is cured, a silicon-containing polymer that is an inorganic material and a linear compound that is an organic material are bonded by a covalent bond. It becomes a mixed chemical bond type composite material. The obtained cured product has properties of both an organic material and an inorganic material, and is particularly excellent in heat resistance, solvent resistance, and alkali resistance. Furthermore, since the chemical bond type curable composition of the present invention is uniform and transparent, it has good light transmittance such as ultraviolet rays and can be photocured.
Furthermore, for weather resistance, hardness, stain resistance, flame resistance, moisture resistance, gas barrier properties, flexibility, elongation and strength, electrical insulation, low dielectric constant, and other mechanical properties, optical properties, electrical properties, etc. An excellent composite material can be obtained.

In addition to the above essential components, the curable component of the present invention is blended with other known additives, fillers, various resins, etc., as optional components, as long as the target performance of the present invention is not impaired. can do.
Various organic functional groups can be bonded to the silicon-containing polymer having a reactive group to give a function. In addition, a highly functional composite material in which other useful compounds are dispersed using the curable composition of the present invention or a cured product thereof as a matrix can be prepared.

【Example】
EXAMPLES Hereinafter, although an Example demonstrates this invention further, this invention is not limited by these Examples. In the examples, “parts” and “%” are based on weight .
Example 1: 72 parts as a solvent of 1-butanol synthesis 72 parts of methyl triethoxysilane silicon-containing polymer A was mixed, after warming to 70 ° C., was added dropwise 22 parts of an aqueous solution 0.12% phosphoric acid. After dripping, it reacted at 80 degreeC for 1 hour. Next, an aqueous sodium hydroxide solution was added to neutralize the reaction solution, followed by reaction at 80 ° C. for 1 hour. 660 parts of 1-butanol was added to 165 parts of the obtained reaction liquid. After adding 800 parts of ion-exchanged water and washing with water three times, the solvent was distilled off at 40 ° C. and 1330 Pa (10 mmHg) under a nitrogen stream to obtain a silicon-containing polymer a. After adding 200 parts of triethyl orthoformate to 40 parts of the resulting silicon-containing polymer a and treating at 130 ° C. for 1 hour, unreacted triethyl orthoformate and the like at 70 to 90 ° C. and 1330 Pa (10 mmHg) under a nitrogen stream. The volatile component was distilled off to obtain a silicon-containing polymer A. As a result of analysis by GPC, the weight average molecular weight was 3700. As a result of analysis by ¹ H-NMR using DMSO-d ⁶ as a solvent, silanol groups (SiOH groups) were not detected. Silicon polymer A was stored at 40 ° C. and its weight average molecular weight after 3 days was 3700, which was not changed.

Example 2: Synthesis of methyltriethoxysilane silicon-containing polymer B (10 parts), phenyltrimethoxysilane (11 parts), and 0.032% phosphoric acid aqueous solution (9.7 parts) were mixed, 3 hours at 10 ° C. did. Further, ethanol (24 parts) was added, an aqueous sodium hydroxide solution was added to neutralize the reaction solution, and the mixture was reacted at 30 ° C. for 15 minutes. Subsequently, triethyl orthoformate (130 parts) was added, and the mixture was stirred at 130 ° C. for 1 hour. Then, add (0.5 parts) of the adsorbent (Kyowa Chemical Industry Kyoward 600S, the same applies below), treat it at 100 ° C, remove the adsorbent by filtration, and then remove the volatile components at 150 ° C and 10 mmHg. To obtain a silicon-containing polymer B. As a result of analysis by GPC, the weight average molecular weight was 3,300. As a result of analysis by ¹ H-NMR using acetone-d ⁶ as a solvent, silanol groups (SiOH groups) were not detected.

Example 3: Synthesis of methyltriethoxysilane silicon-containing polymer C (32 parts) 0.032% phosphoric acid aqueous solution (18 parts) were mixed, after 30 minutes reaction at 10 ° C., vinyltrimethoxysilane (3 parts) The mixture was reacted at 10 ° C. for 30 minutes. Further, an aqueous sodium hydroxide solution was added to neutralize the reaction, and the mixture was reacted at 30 ° C. for 15 minutes. Subsequently, triethyl orthoformate (245 parts) was added and stirred at 130 ° C. for 1 hour. Thereafter, an adsorbent (0.2 parts) was added and the mixture was treated at 100 ° C., and the adsorbent was filtered and removed. Then, the volatile component was distilled off at 80 ° C. and 10 mmHg to obtain silicon-containing polymer C. As a result of analysis by GPC, the weight average molecular weight was 8,400. As a result of analysis by ¹ H-NMR using DMSO-d ⁶ as a solvent, silanol groups (SiOH groups) were not detected.

Example 4: Synthesis of phenyltrimethoxysilane silicon-containing polymer D (40 parts), methyl triethoxysilane (29 parts), and 0.032% phosphoric acid aqueous solution (35 parts), 90 minutes reaction at 10 ° C. Thereafter, vinyltrimethoxysilane (5.9 parts) was added and reacted at 10 ° C. for 30 minutes. Further, ethanol (58 parts) was added and stirred, and then a sodium hydroxide aqueous solution was added to neutralize the reaction solution, followed by reaction at 10 ° C. for 60 minutes. Subsequently, triethyl orthoformate (490 parts) was added, and the mixture was stirred at 130 ° C. for 1 hour. Then, adsorbent (0.4 parts) was added, treated at 100 ° C. for 1 hour, filtered to remove the adsorbent, and then volatile components were distilled off at 80 ° C. and 10 mmHg to obtain a silicon-containing polymer D. It was. As a result of analysis by GPC, the weight average molecular weight was 4,200. As a result of analysis by ¹ H-NMR using acetone-d ⁶ and CDCl ₃ as solvents, silanol groups (SiOH groups) were not detected.

Example 5: Silicon Synthesis methyltriethoxysilane (16 parts) containing polymer E 0.032% phosphoric acid aqueous solution (8.8 parts) were mixed, after 1 hour reaction at 10 ° C., triethoxysilane (1.6 parts) After the addition, the mixture was reacted at 10 ° C. for 2 hours. Further, an aqueous sodium hydroxide solution was added to neutralize the reaction solution, and then reacted at 60 ° C. for 15 minutes. Subsequently, triethyl orthoformate (123 parts) was added, and the mixture was stirred at 130 ° C. for 1 hour. Thereafter, an adsorbent (0.1 part) was added and the mixture was treated at 100 ° C., and the adsorbent was filtered and removed, and then the volatile component was distilled off at 150 ° C. and 10 mmHg to obtain silicon-containing polymer E. As a result of analysis by GPC, the weight average molecular weight was 3,300. As a result of analysis by ¹ H-NMR using DMSO-d ⁶ as a solvent, silanol groups (SiOH groups) were not detected.

Example 6: silicon-containing polymer synthesized methyltriethoxysilane (7.1 parts) of F and phenyltrimethoxysilane (4 parts), and 0.032% phosphoric acid aqueous solution (8.8 parts) were mixed, 1 hour reaction at 10 ° C. Thereafter, triethoxysilane (1.6 parts) was added and reacted at 10 ° C. for 2 hours. Further, an aqueous solution of sodium hydroxide was added to neutralize the reaction solution, and then reacted at 30 ° C. for 1 hour. Subsequently, triethyl orthoformate (123 parts) was added, and the mixture was stirred at 130 ° C. for 1 hour. Thereafter, an adsorbent (0.1 part) was added and the mixture was treated at 100 ° C., and the adsorbent was filtered and removed. Then, the volatile component was distilled off at 150 ° C. and 10 mmHg to obtain silicon-containing polymer F. As a result of analysis by GPC, the weight average molecular weight was 4,900. As a result of analysis by ¹ H-NMR using acetone-d ⁶ as a solvent, silanol groups (SiOH groups) were not detected.

Reference Example 7: Synthesis of silicon-containing polymer G Aminopropyltriethoxysilane (2 parts), water (0.5 parts), and ethanol (7.9 parts) were mixed, reacted at 78 ° C for 1 hour, and then methyltriethoxysilane. (16 parts) was added and reacted at 78 ° C. for 4 hours. Then methyl isobutyl ketone (135 parts) is added and distilled. After the temperature of the reaction solution reached 100 ° C., the mixture was further stirred for 2 hours, and then the solvent was distilled off under reduced pressure. Chloroform (150 parts) and pyridine (9.5 parts) were then added, and trimethylchlorosilane (5.4 parts) was added dropwise, followed by reaction at 50 ° C. for 4 hours. After distilling off the solvent under reduced pressure, toluene (43 parts) was added, the precipitated solid was filtered off, adsorbent (0.1 part) was added, and after treating at 100 ° C., the adsorbent was filtered and removed. Volatile components were distilled off at 150 ° C. and 10 mmHg to obtain a silicon-containing polymer G. As a result of analysis by GPC, the weight average molecular weight was 3,700.

Reference Example 8: Synthesis of silicon-containing polymer H Methyltriethoxysilane (27 parts), phenyltrimethoxysilane (10 parts), and 0.032% phosphoric acid aqueous solution (18 parts) were mixed and reacted at 10 ° C for 2 hours. Thereafter, an aqueous sodium hydroxide solution was added for neutralization, and the mixture was reacted at 40 ° C. for 40 minutes. Next, chloroform (100 parts) was added, dehydrated with sodium sulfate, pyridine (24 parts) was added, and dimethylvinylchlorosilane (24 parts) was added dropwise to react for 1 hour. After the solvent was distilled off under reduced pressure at 40 ° C., toluene (100 ml) was added and the precipitated solid was filtered off, and then the volatile component was distilled off under reduced pressure at 50 ° C. to obtain a silicon polymer H. As a result of analysis by GPC, the weight average molecular weight was 92000. As a result of analysis by ¹ H-NMR using acetone-d ⁶ and CDCl ₃ as solvents, silanol groups (SiOH groups) were not detected.

Reference Example 9: Synthesis of silicon-containing polymer I The same treatment as in Reference Example 8 was conducted except that dimethylchlorosilane (19 parts) was used instead of dimethylvinylchlorosilane (24 parts) and the final vacuum distillation temperature was 100 ° C. Thus, a silicon polymer I was obtained. As a result of analysis by GPC, the weight average molecular weight was 79000. As a result of analysis by ¹ H-NMR using acetone-d ⁶ as a solvent, silanol groups (SiOH groups) were not detected.

Application example 1
Silicon-containing polymer A (7 parts), silanol-terminated diphenylsiloxane-dimethylsiloxane copolymer (3 parts), and dibutyldiacetoxytin (0.01 part) as a curing catalyst were mixed to obtain a transparent curable composition.
After dropping this curable composition onto a glass plate, “room temperature → (10 ° C./min)→150° C. × 10 min → (10 ° C./min)→200° C. × 10 min → (10 ° C./min)→250 C. for 4 hours to obtain a transparent film. The film was uniform and transparent without turbidity.

Application example 2
Silicon-containing polymer B (7 parts), silanol-terminated diphenylsiloxane-dimethylsiloxane copolymer (3 parts), and dibutyldiacetoxytin (0.01 part) as a curing catalyst were mixed to obtain a transparent curable composition.
After dropping this curable composition onto a glass plate, “room temperature → (10 ° C./min)→150° C. × 10 min → (10 ° C./min)→200° C. × 10 min → (10 ° C./min)→250 C. for 4 hours to obtain a transparent film. The film was uniform and transparent without turbidity.

Application example 3
Silicon-containing polymer C (5 parts), H-terminated polydimethylsiloxane (5 parts), and platinum carbonylvinylmethylsiloxane solution (0.01 parts) were mixed to obtain a transparent curable composition.
This curable composition was dropped on a glass plate and then heated at 150 ° C. for 2 hours to obtain a transparent film. The film was uniform and transparent without turbidity.

Application example 4
Silicon-containing polymer C (5 parts), silicon-containing polymer E (5 parts), and platinum carbonylvinylmethylsiloxane solution (0.01 part) were mixed to obtain a transparent curable composition.
This curable composition was dropped on a glass plate and then heated at 150 ° C. for 2 hours to obtain a transparent film. The film was uniform and transparent without turbidity.

Application example 5
Silicon-containing polymer D (5 parts), silicon-containing polymer F (5 parts), and platinum carbonylvinylmethylsiloxane solution (0.01 parts) were mixed to obtain a transparent curable composition.
This curable composition was dropped on a glass plate and then heated at 150 ° C. for 2 hours to obtain a blue transparent film. The obtained film was uniform without transparency and excellent in transparency.

Application example 6
While adding silicon-containing polymer G to bisphenol A type epoxy resin Adeka Resin EP-4100 [Asahi Denka Kogyo Co., Ltd., epoxy equivalent 190] so that the active hydrogen equivalent is 95% of the epoxy equivalent, while cooling Mixed. The mixture was stirred for about 1 minute, applied onto a glass plate, and an aluminum foil was applied thereon, followed by curing at 60 ° C. for 1 hour and then at 120 ° C. for 4 hours. The cured product was uniform and had good heat resistance.

Application example 7
Silicon-containing polymer H (5 parts), silicon-containing polymer I (5 parts), and platinum carbonylvinylmethylsiloxane solution (0.01 parts) were mixed to obtain a transparent curable composition.
This curable composition was dropped on a glass plate and then heated at 150 ° C. for 2 hours to obtain a transparent film. The obtained film was slightly insufficient in flexibility, but was uniform and excellent in transparency without turbidity.

Effect of the invention

  According to the present invention, stability, transparency, and curing performance are excellent, and further, the cured product has excellent physical properties such as heat resistance, solvent resistance, alkali resistance, weather resistance, optical properties, and electrical properties. A composition can be provided.

Claims (1)

^{Si-OR 1, Si-CH} = CH 2, Si-R 2 -CH = CH 2, Si-H, Si-R 2 -NH 2, Si-R 2 -OCOC (R 3) = CH 2 and Si- From the group consisting of R ² —OH groups, wherein R ¹ is an alkyl group having 1 to 5 carbon atoms, R ² is an alkylene group or phenylene group having 1 to 9 carbon atoms, and R ³ is hydrogen or a methyl group. A silicon-containing polymer having one or more selected reactive groups A, no Si-OH groups, one or more cross-linking structures by Si-O-Si bonds, and a molecular weight of 500 to 1,000,000 A manufacturing method of
After obtaining a polymer by hydrolyzing / condensing alkoxysilane or chlorosilane having a reactive group A, the polymer is a kind selected from the group consisting of orthoformate ester, orthoacetate ester, tetraalkoxymethane and carbonate ester Alternatively, a method for producing a silicon-containing polymer, wherein two or more hydrolyzable ester compounds are added, and the Si—OH group of the polymer is sealed by stirring and heating.